Highly Efficient Synthesis of Vinylboron Compounds via Transition Metal Catalyst/Diboron System

1.过渡金属催化剂/二硼体系中乙烯基电子亲核硼化反应乙烯基卤化物或三氟甲磺酸酯与双当PdCl_2（PPh_3）_2-2PPh_3/KOPh/甲苯（50℃）或PdCl_2（PPh_3）_2 - 2PPh_3/K_2CO_3（50℃）时，（频哪醇基）二硼化合物的区域专一性和立体专一性或立体选择性都能得到高收率的乙烯基硼化合物。3/二氧六环，80℃。反应容忍各种官能团，如羰基和氰基。催化循环可涉及乙烯基亲电试剂与钯（0）络合物的氧化加成、二硼和钯（II）中间体之间的金属转移以及乙烯基硼化合物的还原消除。顺序反应，包括亲核硼化的乙烯基亲电试剂与二硼和耦合与不同的乙烯基亲电试剂，提供了一个一锅法合成各种不对称共轭二烯。 ...更多信息 铑催化β-硼基-α，β-不饱和羰基化合物与α，β-不饱和酮的1，4-加成反应得到相应的ω-氧代-α，β-不饱和羰基化合物的高产率研究2.过渡金属催化剂/二硼体系催化烯烃的直接硼化反应当使用1/2[Ir（OMe）（COD）]_2-（4，4 '-二叔丁基-2，2'-联吡啶）/己烷，50℃。该反应伴随有几种副产物，如区域异构体和双（硼基）环己烷。反应可以通过由铱（I）络合物与二硼的反应产生的三（硼基）铱（III）中间体进行。在催化循环中，乙烯基碳-氢键氧化加成到三（硼基）铱（III）络合物上，然后还原消除，或者三（硼基）铱（III）络合物插入到碳-碳双键上，然后β-氢化物消除都可以是有效的。少

1.Nucleophilic Borylation Reactions of Vinylic Electrophrles by Tramsition Metal Catalysts/Diboron SystemNucleophilic borylation reactions of vinylic halides or triflates with bis(pinacolato)diboron regiospesifically and stereospecifically or stereoselectrvely proceeded to afford vinylic boron compounds in excellent yields when using a combination of PdCl_2(PPh_3)_2-2PPh_3/KOPh/toluene at 50℃ or that of PdCl_2(PPh_3)_2-2PPh_3/K_2CO_3/dioxane at 80℃. The reactions tolerated various functionalities such as carbonyl and cyano groups. A catalytic cycle may involve oxidative addition of the vinylic electrophiles to a palladium(O) complex, transmetalation between the diboron and a palladium(II) intermediate, and reductive elimination of vinylic boron compound. Sequential reactions, involving necleophilic borylation of vinylic electrophiles with diboron and coupling with distinct vinylic etectrophiles, provided a one-pot procedure for the synthesis of various unsymmetrical conjugated dienes. … More Rhodium-catalyzed 1,4-addition of β-boryl-α,β-unsaturated carbonyl compounds toα,β-unsaturated ketones afforded the corresponding ω-oxo-α,β-unsaturated carbonyl compounds in high yields.2.Direct Borylation Reactions of Alkenes by Tramsition Metal Catalysts/Diboron SystemA Direct borylation reaction of cyclohexene with bis(pinacolato)diboron proceeded via vinylic carbon-hydrogen bond activation to give 1-boryl-1-cyclohexene in a moderate yield when using a combination of 1/2[Ir(OMe)(COD)]_2-(4,4'-di-tert-buty1-2,2'-bipyridine)/hexane at 50℃. The reaction was accompanied by several by-products such as regioisomers and bis(boryl)cyclohexanes. The reaction may proceed through an tris(boryl)iridium(III) intermediate generated by a reaction of the iridium(I) complex with the diboron. Either oxidative addition of the vinylic carbon-hydogen bond to the tris(boryl)iridium(III) complex followed by reductive elimination or insertion of the tris(boryl)iridium(III) complex to a carbon-carbon double bond followed by β-hydride elimination may be operative in catalytic cycles. Less